Sulfur: A Ubiquitous
and Useful Tracer in
Earth and Planetary Sciences
1811-5209/10/0006-0075$2.50 DOI: 10.2113/gselements.6.2.75
S
ulfur is a widely distributed element on Earth and in the solar system.
Its multiple valence states (S 2- to S6+) allow it to participate in numerous
geochemical and biochemical processes. It may be one of the light
elements in the Earth’s core and may have been crucial in core formation.
Sulfur is an essential component in all life on Earth and likely supported
earliest life. Sulfur geochemistry is used to understand the early evolution
of Earth’s atmosphere and hydrosphere, and serves as a monitor of volcanic
SO2 and H2S and as a tracer of anthropogenic sources of sulfur. Recent advances
in the use of multiple sulfur isotopes (32S, 33S, 34S, and 36S) and in situ isotopic
measurements will help to develop sulfur stable isotopes as a vital tracer in
the Earth and planetary sciences and will provide applications for under-
standing inorganic and biogenic processes.
Keywords: sulfur, stable isotopes, fractionation, sulfides, sulfates, aerosol, tracer
SOME BASIC FACTS ABOUT SULFUR
The word “sulfur” is derived from the Sanskrit sulvere or the
Latin sulphurium. Sulfur was known to the ancients, and in
Genesis it was referred to as brimstone. Sulfur belongs to
Group 16 (more traditionally Group VI), period 3, of the
periodic table of the elements. The Group 16 elements,
including oxygen, selenium, tellurium, and polo- nium, are
referred to as chalcogens, from the Greek words chalcos (ore)
and gen (formation). So the chalcogens, including sulfur,
are ore formers. Sulfur’s classification as an element
probably dates back to the late eighteenth century and the
work of Antoine Lavoisier, though the Chinese knew in the
ninth century that sulfur is a key component of gunpowder,
along with potassium nitrate and carbon. Like other
chalcogens, sulfur commonly has the valence state –2 (S2-).
However, when all the electrons in the outer valence shell
of a sulfur atom are removed, S6+ is formed, which can bond
strongly with oxygen to create the SO 42- anion complex,
called sulfate. Sulfur can also have intermediate valence
states of +4 and +2 and may exist in its native state (S 0).
Variable valence states allow sulfur to participate in
numerous geochemical and biochemical processes.
There are three allotropic forms of native sulfur: two are
crystalline, while one is amorphous and commonly referred
to as plastic sulfur. Sulfur crystals belong either to the
orthorhombic or monoclinic crystal systems. They are
constructed from S 8 molecules that form puckered, eight-
member rings of S atoms. In these rings, the S atoms are
* Dept. of Earth and Planetary Sciences
American Museum of Natural History
Central Park West at 79th Street
New York, NY 10024-5192, USA
E-mail: cmandy@amnh.org
E lEm Ent s, Vol . 6, pp. 75–80
bonded to each other by single
covalent bonds, and the S–S–S
bond angle is approximately 105°
(Mortimer 1977). The ortho-
rhombic allotrope of native sulfur
is the most common (Fig. 1),
whereas the monoclinic allotrope
is rare in nature. Pertinent phys-
ical data for native sulfur are
presented in Table 1. When sulfur is
heated to 200°C and poured into
cold water, a rubbery red-brown
mass called plastic sulfur is
produced. X-ray analysis of plastic
sulfur indicates that it has a molec-
ular structure characteristic of
fibers formed from long chains of
sulfur atoms. When plastic sulfur—a supercooled liquid—is
left at room temperature, it slowly crystallizes and the S8
rings re-form. Sulfur is a poor conductor of thermal energy,
so when you hold crystals of native sulfur near your ear,
you can hear faint cracking noises.
Sulfur is everywhere. It occurs as sulfide minerals in the
Earth’s mantle, as sulfide or sulfate minerals in crustal
rocks, as native sulfur near active or dormant volcanoes, as
dissolved sulfate or dimethyl sulfide in ocean water, and as
a trace gas in the atmosphere. Sulfur is likely one of the light
elements present in the Earth’s Fe–Ni core. It may have
played a key role in the formation of the core because the
melting temperatures of Fe–S mixtures are several
hundred degrees below the melting temperatures of pure Fe
or Fe–Ni alloys, thus facilitating the early differentiation of
Earth into an Fe–Ni core and a largely silicate mantle and
crust. In fact, sulfur is the sixth most abundant element in
the whole Earth (~1.9%) by weight and is exceeded only by
iron, oxygen, silicon, magnesium, and nickel. We also know,
from the presence of sulfide minerals like troilite (FeS) in
iron meteorites and of oldhamite [(Ca,Mg,Fe)S] and
niningerite [(Mg,Fe,Mn)S] in enstatite chondrite and
achondrite meteorites, that sulfur is present in some of the
oldest materials in our solar system—mate- rials that
comprised the building blocks of the terrestrial planets
(Mercury, Venus, Earth, and Mars). Going back in time even
further, sulfur was formed by nucleosynthesis during
explosive oxygen burning in the supernova phase of stellar
evolution (Truran 1973; Clark 1979). 32S, the most common
isotope of sulfur (about 95% of total sulfur), has in its
nucleus the equivalent of eight alpha particles or two 16O
nuclei. We also know from the Voyager, Galileo, and New
Horizons spacecraft missions that Jupiter’s moon Io has
active, tidally driven volcanism that discharges
75 A pr il 2010

Photo of translucent orthorhombic crystals of native
Figure 1 sulfur on aragonite (AMNH 93) from near Cinciana,
Arigento, Sicily. The larger of the two crystals is 3.0 cm in diameter
x 3.7 cm high. Photo By Arthur Singer, courteSy of AmericAn muSeum of
nAturAl hiStory
SO2- and S2-rich plumes tens to hundreds of kilometers in
height (Lopes-Gautier 2000; Spencer et al. 2000) and that Io’s
garishly colored surface is covered by deposits that may be
rich in S3 and S4 molecules. Mars’s regolith and surface rocks
are also sulfur rich (King and McLennan 2010 this issue). So
sulfur is widespread in our solar system and in the universe.
One place you may not have thought of looking for sulfur is
in your own body. In fact, sulfur is an essential ingre- dient
in all forms of life and is a basic component of cysteine and
methionine, necessary for protein synthesis. For example, a
110 kg person has 220 g of sulfur locked up as organosulfur
compounds in fats, body fluids, and skel- etal minerals. It is
not possible to replicate cells without protein synthesis. Also
without cell replication, construc- tion of tissues, organs,
and a complete organism is impossible.
SOURCES, USES, AND PRODUCERS
Anyone who’s been near the rim of an active or extinct
volcano has probably come across native sulfur as veins or
as encrustations formed either as a direct sublimation
product or from the incomplete oxidation of H 2S (sour gas).
Native sulfur can also be formed from sulfates by sulfur-
reducing bacteria. Furthermore, it can be associated with
sulfide minerals resulting from oxidation of the sulfides.
Sulfur is often associated with anhydrite, gypsum, and
calcite in the cap rocks of salt domes, for example, in Texas
and Louisiana.
In the years prior to 1974, much of the production of sulfur
in the United States came from the Gulf Coast region where
sulfur was recovered from the tops of salt domes using the
Frasch process. This method consists of injecting hot water
into the sulfur-containing region in the subsurface, thus
melting the sulfur in place; simultaneously air is injected,
lifting the molten sulfur to the surface. This method of
recovery accounted for approximately 75% of US produc-
E lEm Ent s
tion with the remaining 25% recovered as a by-product from
smelters and petroleum refining. However, the Frasch
process requires significant energy consumption, and the
last processing plant in the United States ceased operation
in 2000 (Ober 2003).
Most of the sulfur produced worldwide is now recovered as
a by-product from petroleum refineries that minimize SO 2
emissions and remove poisonous H 2S from natural gas
supplies. In 2006, the United States was the world’s leading
producer of elemental sulfur, supplying over 9.06 million
metric tons (1 metric ton = 103 kilograms). Canada ranked
second with 9.05 million metric tons. Other major producers
of elemental sulfur, in descending order, include Russia,
Saudi Arabia, United Arab Emirates, Japan, Kazakhstan,
Iran, Germany, and Mexico (Ober 2003, 2007). Countries
producing elemental sulfur as a metallurgical by-product, in
order of decreasing production, are China, Japan, Canada,
Chile, Australia, Korea, Mexico, United States, Russia,
Germany, India, and Spain (Ober 2007).
The most important end use of recovered elemental sulfur is
as a chemical reagent in the manufacture of sulfuric acid.
As a raw material, it is important in all sectors of the world’s
fertilizer and industrial manufacturing processes (Ober
2007). Approximately 50% of consumed sulfur in 2007 was
used in the manufacture of phosphatic, nitrog- enous, and
sulfur fertilizers. The remaining 50% was distributed
among a wide variety of industrial uses and processes,
including the manufacture of pulp and paper products,
inorganic pigments, paints and allied products, industrial
organic chemicals, synthetic rubber and other plastic
materials and synthetics, rubber and plastic prod- ucts,
cellulosic fibers including rayon, water-treatment
compounds, and steel pickling. Other uses include the
processing of copper, zinc, lead, and molybdenum ore; the
manufacture of soaps, detergents, pesticides, and leather
goods; petroleum refining; and the manufacture of petro-
leum and coal products.
Table 1 PROPERTIES OF SULFUR
Sulfur symbol S
Atomic number (Z) 16
Atomic weight 32.065
Melting point 112.8°C (orthorhombic)
Boiling point 444.674°C
Crystallography orthorhombic, 2/m2/m2/m
pyramidal habit common, often with two
dipyramids, prism {011}, and base in
combination; also commonly found in
irregular masses, massive, reniform,
stalactitic, as incrustations, or earthy
Fracture conchoidal to uneven
Hardness 1 ½ to 2 ½
Specific gravity 2.05–2.09
Luster resinous
Color yellow but varies with amount of
impurities to yellowish shades of green,
gray, and red; transparent to translucent
Diagnostic features yellow color and burns easily
Data from Klein and Hurlbut (2002), De Laeter et al. (2003),
and CRC Handbook of Chemistry and Physics (1978)
76 A pr il 2010
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